Detection and Molecular Weight Determination of Organic Vapors

ABSTRACT

Composite films comprising an organic salt (or GUMBOS) such as 1-n-butyl-2,3-dimethylimidazolium hexafluoro-phosphate and a polymer such as cellulose acetate are prepared. These films are useful in detecting vapors of volatile organic compounds, and in determining their molecular weights. A quartz crystal microbalance-based sensor was designed by depositing a thin film of this composite material on the gold electrode surface of a quartz crystal resonator. The sensor exhibited rapid response toward a variety of volatile organic compounds, and complete regeneration, high sensitivity, low detection limits, and wide dynamic ranges. The ratio of the change in frequency to the change in motional resistance is a concentration-independent quantity that is proportional to the molecular weight of the absorbed chemical species. These properties facilitate the easy identification and molecular weight determination of a broad range of organic vapors.

This is the United States national stage of international applicationPCT/US2012/021806, international filing date Jan. 19, 2012, which claimsthe benefit of the Jan. 20, 2011 filing date of U.S. provisional patentapplication Ser. No. 61/434,660; and of the Jan. 21, 2011 filing date ofU.S. provisional application Ser. No. 61/434,879 under 35 U.S.C.§119(e). The complete disclosures of both priority applications arehereby incorporated by reference in their entirety.

This invention was made with government support under grant CHE-0911118awarded by the National Science Foundation, and grant 1R01GM079670awarded by the National Institutes of Health. The United StatesGovernment has certain rights in this invention.

TECHNICAL FIELD

This invention pertains to GUMBOS-based composite materials, and theiruse for detection and molecular weight determination of gases.

BACKGROUND ART

The development of cost-efficient, portable, and sensitive detectionsystems for volatile organic compounds (VOCs) has become increasinglyimportant. VOC sensors have extensive utility in environmentalmonitoring, health care, agriculture, food safety, defense, and homelandsecurity applications. Many sensing technologies have been used fordetection of VOCs, including differential ion mobility spectrometry, gaschromatography-mass spectrometry, photoionization, laser desorption massspectrometry, nanowire coatings, and cantilever detectors. Devices basedon the sorption of gas molecules are increasingly being adopted becauseof their simplicity, compactness, and amenability to use with sensorarrays. Sorption-based sensors have a chemosensitive coating thatselectively and reversibly sorbs analytes of interest. To achieveoptimal measurement of the analyte, sensing materials are oftenimmobilized directly onto the surface of a transducer that converts thebinding event into an electronic signal. Mechanical oscillators,chemicapacitors, and chemiresistors are often the transducers of choicefor analyses of a broad range of chemical vapors.

A quartz crystal microbalance (QCM) is a common piezoelectric transducerthat can be used as a sorption-based sensor. The operating principle ofthis sensor is based on the alteration of the characteristics ofacoustic shear waves propagating through the piezoelectric material. AQCM typically comprises a thin slice of AT-cut quartz wafer that issandwiched between two electrodes. When an oscillating electric voltageis applied perpendicular to the surface of the quartz resonator, anacoustic shear wave is produced that propagates across the thickness ofthe crystal. As the sorbent coating interacts with the analyte, its massand mechanical properties are altered, which in turn leads to a phaseshift and attenuation of the shear wave propagating through the filmadhering to the electrode surface. This phase shift leads to a change inresonance frequency, which depends on the mass of added material on thesurface of the resonator. The frequency shift, Δf, and the added mass,Δm, of the analyte are related according to the Sauerbrey equation:

$\begin{matrix}{{\Delta \; f} = {{- \frac{2\; \Delta \; {mf}^{2}}{{A\left( {\mu \; \rho_{q}} \right)}^{\frac{1}{2}}}} = {{- C_{f}}\Delta \; m}}} & \left( {{Equation}\mspace{14mu} 1} \right)\end{matrix}$

where f is the intrinsic frequency of the quartz crystal, A is theactive vibrating area, μ is the shear modulus of quartz (2.95×10¹¹dyne/cm²), ρ_(g) is the density of quartz (2.65 g/cm³), and C_(f) is theintegrated QCM sensitivity (i.e., collecting all the factors except Δm).The Sauerbrey equation is valid in the regime where the adsorbed mass issmall as compared to the overall mass of the crystal, and the additionalmass is rigidly bound and evenly distributed over the electrode'ssurface. Attenuation of the shear wave is due to dissipation of energyduring oscillation. This attenuation can be estimated by measuring anelectrical property called motional resistance, R, of the QCM. Thin andrigid films display less dissipation and hence produce a small increasein R, while thick and viscoelastic films exhibit high dissipation and acorrespondingly large increase in R.

Various sensing materials, including polymers, inorganic oxides,polymer/carbon black composites, carbon nanotubes, graphitemicroparticles, amino acids, TiO₂-porphyrin nanocomposites, calixarenes,lipids, and room temperature ionic liquids (RTILs), have been used informulating chemosensitive QCM coatings to detect and identify a rangeof VOCs.

Ionic liquids (ILs) are usually defined as organic salts that melt below100° C. ILs that are liquid at or below room temperature are commonlyknown as RTILs, whereas those in the solid state, i.e. room temperatureto 100° C., are often referred to as ‘frozen’ ILs.

The use of RTILs as sensing materials is relatively recent. The uniquecombination of thermal and chemical stability with tunablephysico-chemical properties has led to the use of RTILs for gas sensingapplications. Short response time and high reversibility are propertiesof QCM/RTIL sensors. However, the use of RTILs as gas sensors has twomajor limitations: de-wetting of a film coating to form macroscopicdrops; and the well-known viscosity-density effect. The absorption oforganic vapor into RTILs causes a decrease in the density and viscosityof the liquid, leading to an increase in frequency—the so-calledviscosity-density effect. To overcome these drawbacks, very thin RTILcoatings have sometimes been used. The thin coatings behave asquasi-rigid layers, and hence exhibit a decrease in frequency uponanalyte sorption. The use of thin films, however, limits the sensitivityof the sensor, because the amount of vapor that can be absorbed dependson the quantity of the sorbent material deposited on the surface.

“GUMBOS” are compounds from a Group of Uniform Materials Based onOrganic Salts. The acronym GUMBOS includes both frozen ILs (those withmelting points from 25° C. to 100° C.) and analogous organic salts thatmelt from 100° C. to 250° C. See A. Tesfai, B. El-Zahab, A. T. Kelley,M. Li, J. C. Garno, G. A. Baker, I. M. Warner, ACS Nano 2009, 3, 3244;and published international patent application WO 2009/082618. “GUMBOS”is defined to mean an organic salt having a melting point between 25° C.and 250° C. (The word “GUMBOS” may be either singular or plural.)

A. F. Holloway, A. Nabok, M. Thompson, A. K. Ray, D. Crowther, J.Siddiqi, Sensors 2003, 3, 187 reported using calyx[4]resorcinarene filmswith QCM to measure Δf and ΔR, distinguishing between hexane and toluenevapors. While the authors reported measurements of Δf and ΔR, they didnot report any correlation between Δf/ΔR and the physico-chemicalproperties of the analytes.

DISCLOSURE OF THE INVENTION

We have discovered novel composite materials and methods for thedetection, discrimination, and molecular weight determination of organicvapors via piezoelectric measurements. The novel apparatus and methodemploy a composite film containing one or more GUMBOS, deposited on apiezoelectric crystal microbalance. The novel apparatus and method haveexcellent properties for detecting and characterizing organic vapors.

Besides the GUMBOS component, the other component of the composite(typically a polymer) acts to inhibit crystallization of the GUMBOS andto modulate the viscoelastic properties of the GUMBOS, so that thecomposite has a linear relationship between Δf/ΔR and the molecularweight of absorbed compounds. The composite material is viscoelastic;and the viscoelastic characteristics of the composite material aresubstantially different from what the viscoelastic characteristics ofthe GUMBOS alone would be, if the GUMBOS were not intermixed with one ormore polymers. The GUMBOS is amorphous within said composite material.In our prototype embodiment, the other component of the composite was apolymer, cellulose acetate. We believe that the cellulose acetateprovided a fibrous scaffold upon which the GUMBOS could deposit, and indoing so improve the viscoelastic behavior of the film. In addition tocellulose acetate, we have also seen similar behavior with celluloseacetate butyrate. Other polymers known in the art may also be used informing GUMBOS-containing composites. Preferred polymers for thispurpose are polyelectrolytes, or polymers otherwise containing polargroups; but even nonpolar polymers may be used in forming thecomposites. Preferred polyelectrolytes, include for example thefollowing polycations and polyanions:

Polycations:

-   Poly(allylamine)-   Poly(2-ethyl-2-oxazoline)-   Poly(acrylamide-co-diallyldimethylammonium chloride)-   Poly[bis(2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl]urea]quaternized-   Poly(dimethylamine-co-epichlorohydrin-co-ethylenediamine)-   Poly(2-dimethylamino)ethyl methacrylate) methyl chloride-   Poly(p-xylene tetrahydrothiophenium chloride)-   Poly(diallyldimethylammonium chloride)-   Poly-L-Lysine-   Poly(ethyleneimine)-   Poly(amido amine) dendrimer-   Poly-L-ornithine-   Polybrene-   Poly-arginine-   Chitosan

Polyanions:

-   Poly(vinyl sulfate)-   Poly(sodium 4-styrenesulfonate)-   Polyanetholesulfonic acid-   Poly(4-styrenesulfonic acid-co-maleic acid)-   Poly(2-acrylamido-2-methyl-1-propanesulfonic acid)-   Poly(2-acrylamido-2-methyl-1-propanesulfonic acid-co-acrylonitrile)-   Polyinosinic-polycytidylic acid-   Poly(methacrylic acid)-   Poly(styrenesulfonic acid)-   Poly(vinylsulfonic acid, sodium salt)-   Poly[1-[4-(3-carboxy-4-hydroxyphenylazo)benzenesulfonamido]-1,2-ethanediyl,    sodium salt]-   Poly(2′-deoxyadenylic acid)-   Poly(deoxyadenylic-thymidylic) acid-   Poly-D-glutamic acid-   Poly(ethylene-co-methacrylic acid)-   Polycytidylic acid-   Poly-L-aspartic acid-   Poly(guanylic-uridylic) acid

In a prototype embodiment, we have prepared, investigated, andcharacterized the vapor sensing characteristics of a thin composite filmcomprising cellulose acetate (CA), which has a glass transitiontemperature of 67° C., and a representative GUMBOS:1-n-butyl-2,3-dimethylimidazolium hexafluorophosphate ([BM₂Im][PF₆]),which has a melting point of 43° C. and a glass transition temperatureof −58° C. A film of the composite material on a gold substrate wasprepared by co-deposition of [BM₂Im][PF₆] and CA. The film has beencharacterized by scanning electron microscopy (SEM), laser scanningconfocal microscopy (LSCM), powder X-ray diffraction (XRD), Fouriertransform infrared (FTIR) spectroscopy, and electron probe microanalysiswith wavelength dispersive spectroscopy (EPMA-WDS). Classical moleculardynamics (MD) simulations for systems containing [BM₂Im][PF₆], CA, andone of several VOCs were also performed to theoretically model theinteractions between these species.

The novel thin composite films have been deposited as a composite ontothe gold electrode of a QCM device, which has then successfully beenused for detecting and discriminating VOCs. The response of theresultant QCM sensor toward a variety of organic vapors was measured.The novel composite-coated sensor exhibited rapid response, highsensitivity, low detection limits, wide dynamic ranges, and completeregeneration. Changes in the viscoelastic properties of the film uponsorption of various analyte vapors were determined by simultaneouslymonitoring both Δf and motional resistance shift (ΔR). Analysis of thesedata at low to moderate vapor absorptions revealed the surprisingdiscoveries that the ratio Δf/ΔR is nearly constant for a particularvapor, and that this ratio depends directly upon the molecular weight ofthe absorbed chemical species. This surprising finding allows QCM withGUMBOS composite films to be used in identifying and quantifying a widevariety of analytes.

While quartz is preferred, other crystals of other piezoelectricmaterials known in the art may also be used in practicing thisinvention, including for example gallium orthophosphate or langasite.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1( a)-(c) depict SEM micrographs of GUMBOS films deposited on goldsurfaces. FIG. 1( a) depicts a film of approximately 73 μg/cm²[BM₂Im][PF₆] alone. FIG. 1( b) depicts a film of approximately 83 μg/cm²of the [BM₂Im][PF₆]/CA composite. FIG. 1( c) depicts a film ofapproximately 214 μg/cm² of the [BM₂Im][PF₆]/CA composite.

FIG. 2( a) depicts attenuated total reflectance Fourier transforminfrared (ATR-FTIR) spectra of CA, [BM₂Im][PF₆], and [BM₂Im][PF₆]/CAfilms. FIG. 2( b) depicts the changes in the IR spectra of the hydroxyland carbonyl bands. The inset in FIG. 2( b) depicts a magnified plot ofthe 1760-1730 cm⁻¹ region.

FIG. 3( a) depicts the frequency shift as a function of acetonitrilevapor concentrations for three different coatings: the first preparedusing [BM₂Im][PF₆] only; the second one being a composite with celluloseacetate, having the same concentration (in solution) of [BM₂Im][PF₆] asthe first, at a mass ratio of 7.5:1; and the third prepared with thesame concentration of cellulose acetate (in solution) as in thecomposite, but without any [BM₂Im][PF₆].

FIG. 3( b) depicts ΔR at different concentrations of acetonitrile for[BM₂Im][PF₆] and [BM₂Im][PF₆]/CA films.

FIG. 3 c depicts plots of motional resistance shift versus frequencychange for [BM₂Im][PF₆] and [BM₂Im][PF₆]/CA films on exposure to varyingconcentrations of acetonitrile.

FIG. 4 depicts a plot of the frequency shift as a function of vaporconcentration for each of six VOCs.

FIG. 5 depicts the frequency and resistance responses of a prototype QCMsensor to four different concentrations of chloroform vapor over acourse of time: (a) 17.8 mg/L, (b) 35.6 mg/L, (c) 53.4 mg/L, and (d)71.3 mg/L. The amount of coating material was 207 μg/cm². The uppercurve depicts motional resistance response, and the lower curve depictsfrequency response.

FIG. 6( a) depicts a plot of Δf versus ΔR for eight VOCs. The amount ofcoating material was 83 μg of composite film per cm² of electrode area.

FIG. 6( b) depicts a plot of the ratio Δf/ΔR versus molecular weight foreach of the eight compounds using the same film as in FIG. 6( a).

FIG. 7 depicts a schematic diagram of the experimental setup.

FIG. 8 depicts Δf, ΔR, response time, and regeneration time forchloroform vapor.

FIG. 9 depicts, for the same data given in FIG. 6( a), a plot of ΔRversus nanomoles of compound absorbed per square centimeter.

MODES FOR CARRYING OUT THE INVENTION Materials and Methods Example 1Materials

-   [BM₂Im][PF₆], [BM₂Im][OTf], and [BMPyr][PF₆] were obtained from    Ionic Liquids Technologies, Inc. as crystalline solids. [EM₂Im][PF₆]    (crystalline solid), cellulose acetate (molecular weight 30,000 Da),    cellulose acetate butyrate (molecular weight 30,000 Da), anhydrous    heptane, anhydrous acetonitrile, anhydrous chloroform, anhydrous    carbon tetrachloride, and anhydrous toluene were obtained from    Sigma-Aldrich. Acetone, n-propanol, and anhydrous methanol were    obtained from Mallinckrodt Chemicals, and absolute ethanol was    obtained from Pharmco. All reagents were used as received.

The QCM200 controller and associated quartz crystals were purchased fromStanford Research Systems, Inc., Sunnyvale, Calif. The crystals were5-MHz AT-cut chromium/gold polished crystals, 1.00 inch (2.54 cm)diameter. Gold-coated silicon wafers were obtained from Sigma Aldrich.Polytetrafluoroethylene (PTFE) containers used in these experiments wereobtained from SPI Supplies/Structure Probe, Inc. United States.

Example 2 Preparation of Stock Solutions

Stock solutions of [BM₂Im][PF₆] (1 mg/mL) and cellulose acetate (0.5mg/mL) in acetone were prepared in 20-ml borosilicate glassscintillation vials. Particulate matter was removed by successivefiltration using a glass syringe with a stainless steel filter holderand a Whatman 0.45 μm PTFE/GMF syringe filter.

Example 3 Cleaning of Gold Surface

The QCM crystal (or gold-coated silicon wafer) was rinsed with distilledwater and ultrasonicated in acetone for 5 minutes; and then dried underflowing nitrogen gas. The crystal was then immersed in fresh “piranha”solution (3:1 concentrated sulfuric acid and 30% hydrogen peroxide) for10 minutes, washed with copious amounts of distilled water, rinsed withacetone, and dried under a stream of nitrogen. The crystal was furtherdried in an oven at 100° C., and allowed to cool to room temperature.Cleaned crystals were coated immediately.

Example 4 Preparation of Films

Coatings were prepared by a solvent precipitation method. To 2 mL of asolution containing various concentrations of [BM₂Im][PF₆], 6 mL ofanhydrous heptane was added dropwise with stirring. (In the case of thecomposite, the mass proportion of [BM₂Im][PF₆] and cellulose acetate inthe solution was initially varied. The optimal mass [BM₂Im][PF₆]-to-CAmass ratio was found to be about 7.5:1, a ratio that was then maintainedin further experiments.) The mixture was then transferred to a 25-mLPTFE beaker. A cleaned quartz crystal was immersed in the mixture andallowed to incubate for six hours. The crystal was then ultrasonicatedfor one minute, while being held vertically in a fresh pool of heptane,to remove any loosely adhered material. The coated crystal was thenstored in a desiccator for a minimum of 24 hours before being mounted inthe crystal holder. A similar procedure was used for coating the surfaceof the gold-coated silicon substrate.

Example 5 Characterization of Film Coatings

SEM Analysis:

A film was imaged using a JEOL JSM-6610 scanning electron microscope inhigh-vacuum mode.

LSCM Analysis:

The heights of the droplets were analyzed using a Leica TCS SP2 laserscanning confocal microscope in reflection mode, using a 488-nm laser.

Powder X-Ray Diffraction Analysis:

Powder XRD data of the films deposited on gold surface or glass surfacewere collected using a Bruker/Siemens D5000 automated powder X-raydiffractometer, using Cu Kα radiation and a scintillation pointdetector. The operating conditions were set at 40 kV and 30 mA, and thedata were recorded over a 20 range from 2° to 70° at intervals of 0.02°,taken at 1 second per step.

FTIR Analysis:

IR spectra of the films were recorded on a Bruker Tensor 27 spectrometerequipped with a PIKE MIRacle single-bounce attenuated total reflectance(ATR) cell. Spectra were collected over the 3600-530 cm⁻¹ region with256 scans at a resolution of 4 cm⁻¹. FTIR data were analyzed using OPUS6.5 software.

Electron Probe Microanalysis:

EPMA of the films was performed with a JEOL Superprobe 733, equippedwith a wavelength dispersive spectrometer (WDS), using an acceleratingvoltage of 15 kV, a probe current of 10 nA, and a beam diameter of 30microns. Nine different spots in each film and a blank substrate wereanalyzed.

Example 6 Data Acquisition

The QCM sensor was exposed to various VOC vapors in a custom-madenon-flow system. A schematic diagram of the experimental setup isdepicted in FIG. 7. The volume of the chamber 2, less the volume ofcrystal holder 4, was 4.14 L. The volumes of the fan 6 and filter paper8 were disregarded. Chamber 2 contained an inlet 10 and an outlet 12 forargon gas; and a rubber septum 14 for sample introduction. Ultrapureargon was intermittently blown through the container until stablefrequency and motional resistance were obtained. After achievingequilibrium, the argon inlet and outlet were closed; and a known volumeof liquid organic sample was injected into the closed container 2 usinga Hamilton microsyringe (not shown). The rate of evaporation wasenhanced by dropping the sample onto filter paper 8, and the vapor washomogenized using small fan 6. The frequency and resistance shifts ofcoated crystal 16, which was driven by QCM25 crystal oscillator 18, weremeasured following the introduction of analyte vapor. The data 20 wereoutput to a QCM200 digital controller and a digital computer (notshown). The static capacitance, C_(o), of the instrument was nullifiedto obtain the true values of resonance frequency and motionalresistance. The concentration of analyte was successively increased toproduce a response curve. The introduction of analyte into the chamberproduced an increase in overall pressure, but this small pressure changewas found to have a negligible effect on both frequency and motionalresistance. All experiments were performed in a temperature-controlledroom at 22° C. Temperature fluctuations during experiments were measuredto be below ±0.2° C. Sample vapors were removed following a measurementby blowing a gentle stream of ultrapure argon gas through the containeruntil the baseline values were recovered.

Example 7 Molecular Dynamics Simulations

Classical MD simulations were performed with the GROMACS MD package inthe NPT ensemble. See B. Hess, C. Kutzner, D. van der Spoel, E. Lindahl,J. Chem. Theory Comput. 2008, 4, 435. The isotropic pressure couplingwith a time constant of 0.2 ps was controlled by a Berendsen barostat.The improved velocity-rescaling algorithm recently proposed byParrinello et al. was used to mimic weak thermal coupling with acoupling constant of 0.05 ps. See G. Bussi, D. Donadio, M. Parrinello,J. Chem. Phys. 2007, 126, 014101; and G. Bussi, T. Zykova-Timan, M.Parrinello, J. Chem. Phys. 2009, 130, 074101. In all simulations,Lennard-Jones interactions were cutoff at 1.2 nm, and long-range Coulombinteractions were handled by the particle-mesh Ewald (PME) method with acutoff of 1.0 nm and a grid spacing of 0.1 nm. See D. Y. Tom Darden, andLee Pedersen, J. Chem. Phys. 1993, 98, 10089. Periodic boundaries wereapplied in all directions. In all simulations, H-bond lengths wereconstrained with the LILACS algorithm. See B. Hess, H. Bekker, H. J. C.Berendsen, J. Fraaije, J. Comput. Chem. 1997, 18, 1463.

The system modeled in these simulations contained 500 pairs of[BM₂Im][PF₆], and 18 oligomers of CA, with a mass ratio between the twoof 7.5:1 (the same as that of the experiments). A single molecule ofanalyte was added to the simulation box. Six different analytes used inthe experiments were considered in different simulations: acetone,acetonitrile, chloroform, ethanol, methanol, and toluene. All parametersused for modeling were selected from force fields available in theliterature. Intramolecular parameters (bond lengths, valence angles, andtorsional profiles) and intermolecular parameters (Lennard-Jones termsand electrostatic charges) were chosen from the OPLS-AA force field for[BM₂Im]⁺, [PF₆]⁻, CA, and the six analytes. See W. L. Jorgensen, D. S.Maxwell, J. Tiradorives, J. Am. Chem. Soc. 1996, 118, 11225 Coulombinteractions were represented by partial charges placed on the atomicsites as defined by Lopes and Padua and Jorgensen. See J. N. C. Lopes,J. Deschamps, A. A. H. Padua, J. Phys. Chem. B 2004, 108, 2038; J. N. C.Lopes, A. A. H. Padua, K. Shimizu, J. Phys. Chem. B 2008, 112, 5039; andW. L. Jorgensen, D. S. Maxwell, J. Tiradorives, J. Am. Chem. Soc. 1996,118, 11225.

Simulations were performed at 350° K, a temperature at which[BM₂Im][PF₆] is in the liquid phase. By running the simulation at such ahigh temperature, all molecules in the system had greater thermalmobility, thus allowing the sampling of properties of interest usingshorter simulations. The simulations were run at 350° K for 2 ns forequilibration, and the properties of interest were then observed duringanother 2 ns. We also ran two, 4 ns simulations at 295° K (the actualexperimental temperature), and found minimal changes in the trends ofthe properties of interest. To determine the electrostatic and van derWaals energies in GROMACS, the following energy groups were defined: themolecule of VOC, the ions [BM₂Im]⁺, [PF₆]⁻, the CA groups; a single ionof [BM₂Im*]⁺, a single [PF₆*]⁻ ion, and a single CA oligomer, allrandomly chosen. The total interaction energy of any given molecule ofVOC with the other species in the system (all the [BM₂Im]⁺ and [PF₆]⁻ions; and all oligomers of CA) was computed in the simulations. Thetotal interaction energy was compared against the total interactionenergies experienced by one [BM₂Im]⁺ cation, one [PF₆]⁻ anion and one CAoligomer in the system.

Results and Discussion

The films were prepared using a solvent precipitation method. Thechemical constituents that would form the film were dissolved in abinary liquid mixture containing a volatile solvent (acetone) and a lessvolatile non-solvent (heptane). The non-solvent did not itself dissolvethe film-forming constituents. However, it was miscible with thesolvent. Preferential evaporation of the solvent left a thin filmdeposited on the substrate. Both [BM₂Im][PF₆] and [BM₂Im][PF₆]/CAcomposite films were studied, with the former being used primarily forcomparison purposes. In the case of the composite, the mass proportionof [BM₂Im][PF₆] and CA was kept at 7.5:1, which we had determined to bea preferred ratio.

Example 8 Characterization by Scanning Electron Microscopy

FIGS. 1( a)-(c) display SEM micrographs of films deposited on goldsurfaces. FIG. 1( a) depicts a film of approximately 73 μg/cm²[BM₂Im][PF₆] alone. FIG. 1( b) depicts a film of approximately 83 μg/cm²of the [BM₂Im][PF₆]/CA composite. FIG. 1( c) depicts a film ofapproximately 214 μg/cm² of the [BM₂Im][PF₆]/CA composite.

It is evident from FIGS. 1( a)-(c) that the films were discontinuous,and that they contained isolated microdroplets with a variable sizedistribution. The shapes of the droplets for pure [BM₂Im][PF₆] were moreregular than those in the composite films. While the droplets may appearto be liquid in the images, we observed that the coating was physicallystable and solid. The decrease in frequency and increase in motionalresistance observed upon exposure of the films to organic vapors duringQCM measurements (discussed below) strongly support the conclusion thatthe films were in the solid state. By contrast, had the films beenliquid, under such high loading conditions the absorption of organicvapor would have produced a positive frequency shift due to a decreasein the viscosity and density of the liquid. Furthermore, a drop in theviscosity and density of a liquid would be expected to decrease themotional resistance, contrary to our actual observations. The height ofthe droplets, as measured by LSCM, was found to increase with the size(or radius) of the droplets. The maximum height of [BM₂Im][PF₆] dropletsunder intermediate loading conditions (FIG. 1 a) was approximately 2.6p.m. The maximum height of the [BM₂Im][PF₆]/CA droplets under similarloading conditions (FIG. 1 b) was approximately 2.8 μm. FIG. 1 c is animage of the composite film under high loading conditions, showing thatthe droplets grew in size as the amount of coating material increased.In FIG. 1 c the maximum height was approximately 3.2 μm.

Example 9 Characterization by Powder X-Ray Diffraction

Powder XRD measurements of the films deposited on gold-silicon did notreveal any additional peak(s) beyond those of the substrate (data notshown). This observation suggested that both the [BM₂Im][PF₆] film andthe [BM₂Im][PF₆]/CA film were amorphous. To confirm that there were nocoincidental overlaps between diffraction peaks of the films and thoseof the underlying gold-silicon substrate, films were also prepared on anamorphous glass substrate. The XRD patterns of the films on the glasssubstrate did not display any sharp peaks, confirming that the filmswere amorphous (data not shown).

Example 10 Characterization by Infrared Spectroscopy

Attenuated total reflectance Fourier transform infrared (ATR-FTIR)spectra of CA, [BM₂Im][PF₆], and [BM₂Im][PF₆]/CA films are shown in FIG.2( a). CA can be identified though strong absorption bands with peaks at1743-1744 cm⁻¹ (C═O stretch), 1370 cm⁻¹(C—H bending), 1233 cm⁻¹ (C-0stretch, acetyl), and 1051 cm⁻¹ (C—O stretch, pyranose ring).[BM₂Im][PF₆] can be identified though its absorption bands at 3188 cm⁻¹and 3156 cm⁻¹ (C—H stretching vibrations of imidazolium ring); 2968cm⁻¹, 2945 cm⁻¹ and 2881 cm⁻¹ (CH₃ stretching); 1592 cm⁻¹ (C═Cstretching); 1469 cm⁻¹ (CH₃ bending); 833 cm⁻¹ (P—F stretching); and 558cm⁻¹ (F—P—F bending). Absorption bands from [BM₂Im][PF₆] and from CAwere observed in the IR spectrum of the composite film. However, theintensity of the broad band centered around 3500 cm⁻¹ (hydroxyl region)decreased, and the C═O stretching band was blue shifted by 9-10 cm⁻¹ inthe composite film as compared to the corresponding bands for the pureCA film, as shown in FIG. 2 b. FIG. 2 b depicts the changes in the IRspectra of hydroxyl and carbonyl bands. The inset in FIG. 2 b depicts amagnified plot of the 1760-1730 cm⁻¹ region. These observationssuggested a disruption of some of the hydrogen bonds between CAmolecules, and a change in the environment of carbonyl groups. The IRpatterns of [BM₂Im][PF₆], however, showed no strong differences betweenpure and composite films.

Example 11 Characterization by Electron Probe Microanalysis—WavelengthDispersion Spectroscopy

The [BM₂Im][PF₆]-to-CA ratio in the composite film was measured byelectron probe microanalysis—wavelength dispersion spectroscopy(EPMA-WDS). The phosphorus-to-oxygen (P:O) ratios at nine different30-μm spots were analyzed. Based on the total P:O ratio, the mass ratioof [BM₂Im][PF₆] to CA in the film was found to be approximately 7.8:1.Some oxygen background was observed in both the [BM₂Im][PF₆] film andthe blank substrate (gold-coated silicon). Only the “excess” oxygen inthe [BM₂Im][PF₆]/CA film as compared to that in the [BM₂Im][PF₆] filmwas attributed to cellulose acetate. Clear variations of P:O ratios werenoted in some spots, indicating a heterogeneous distribution of[BM₂Im][PF₆] and CA on the surface.

Example 12 Evaluation of Vapor Sensing Properties of Films

We evaluated the chemical-sensing properties of the novel films using aQCM transducer. Thin films were deposited on the gold electrode surfaceof the quartz crystal resonator, and we then measured the frequency andresistance responses of the sensor upon exposure to various VOCs. FIG.3( a) depicts the frequency shift as a function of acetonitrile vaporconcentrations for three different coatings: the first prepared using[BM₂Im][PF₆] only; the second one being a composite with celluloseacetate, having the same concentration (in solution) of [BM₂Im][PF₆] asthe first, at a mass ratio of 7.5:1; and the third prepared with thesame concentration of cellulose acetate (in solution) as in thecomposite, but without any [BM₂Im][PF₆]. The approximate mass loadscalculated from the Sauerbrey equation (Eqn. 1) were 139 μg/cm² for[BM₂Im][PF₆], 176 μg/cm² for [BM₂Im][PF₆]/CA, and 3 μg/cm² for CA alone.For the [BM₂Im][PF₆]-only film, Δf was substantially smaller inmagnitude, and decreased at higher concentrations of acetonitrile. Inother words, above a certain vapor concentration, the observed frequencyincreased with further increases in the vapor concentration. Similarnon-Sauerbrey behavior has been observed by others during CO₂ absorptiononto sugar acetate film, where it has been ascribed to deliquescence;and following moisture adsorption onto ZnO nanowire and ZnS nanowirefilms, where it was attributed to a decrease in the mechanical stiffnessof the films. In marked contrast, as seen in FIG. 3( a) the[BM₂Im][PF₆]/CA film showed excellent linearity over a wide range ofconcentrations. Attempts were made to coat only CA using a similarprocedure; however, a comparatively low mass loading resulted, one thatproduced a negligible frequency response. Note that this response wasone that would still have been very low even if it had been linearlynormalized to the amount of cellulose acetate in the composite.

To better understand the reasons for enhanced performance of the[BM₂Im][PF₆]/CA film, we simultaneously measured Δf and ΔR for both[BM₂Im][PF₆] and [BM₂Im][PF₆]/CA films upon sorption of acetonitrilevapors. As shown in FIG. 3 b in both cases ΔR increased as a function ofacetonitrile concentration. FIG. 3 c depicts a plot of motionalresistance shift versus frequency change for [BM₂Im][PF₆] and[BM₂Im][PF₆]/CA films on exposure to varying concentrations ofacetonitrile. However, as shown in FIG. 3 c the ratio ΔR/Δf was muchhigher for [BM₂Im][PF₆] than that for the [BM₂Im][PF₆]/CA film. The datain FIG. 3 c imply that the [BM₂Im][PF₆]/CA film was substantially morerigid than the [BM₂Im][PF₆] film. (In each of FIGS. 3 a, 3 b, and 3 c,the legends indicate the mass of film material on the QCR surface, inμg/cm².)

Example 13 Results of Molecular Dynamics Modeling

Our MD simulations showed that acetonitrile had negligible electrostaticand van der Waals interactions with CA. By contrast, strongerinteractions occurred between acetonitrile and the [BM₂Im]⁺ and [PF₆]⁻ions (data not shown). Similar trends were also seen in the simulationsfor other analytes (data not shown). Taken in aggregate, theseobservations implied that the sorption characteristics of the compositefilm were primarily attributable to [BM₂Im][PF₆], while the CA played animportant role in improving the mechanical stiffness of the material.This increase in rigidity can be qualitatively rationalized using thesimple ‘rule-of-mixtures,’ which is often used to estimate themechanical response of a composite material from the properties andconcentrations of its individual constituents. Our data led us toconclude that the [BM₂Im][PF₆]/CA composite film (7.5:1 mass ratio) ispreferred for QCM-based vapor sensing. This preferred composite was usedin testing various sensing applications of the film.

Example 14 Effects of Mass of Composite Material on Sensitivity

The sensitivity of the sensor (the change in the sensor's resonancefrequency per unit change in analyte concentration) was observed toincrease linearly with the amount of sensing material loaded onto thesurface of the resonator (i.e., the mass per unit area; data not shown).The linear relationship between frequency shift and vapor concentration,and the linear relationship between the sensitivity and amount ofsensing material indicated that the mass transfer process at theinterface was predominantly the bulk absorption of vapors by the coatingmaterial. The mass of the sensing material deposited onto the resonatorwas controlled by changing the concentrations of [BM₂Im][PF₆] and CA (ata constant mass ratio), while holding the volumes of solvent andnon-solvent constant. The maximum amount we loaded in this set ofexperiments was approximately 214 μg of the composite material per cm²of the electrode surface. While it would be possible to increase themass loading further using the same coating procedure, higher massloadings slowed the response, are thought to be less preferred, and werenot studied in detail.

In marked contrast to the linear responses we observed using the novelGUMBOS composites, it has been reported that for RTILs, the sensitivityplateaus or the frequency change even becomes positive when thethickness of the coating exceeds ˜200 nm, corresponding to a mass loadof ˜20-25 μg/cm². See, e.g., X. X. Jin, L. Yu, D. Garcia, R. X. Ren, X.Q. Zeng, Anal. Chem. 2006, 78, 6980; and X. M. Xu, H. W. Cang, C. Z. Li,Z. B. K. Zhao, H. Y. Li, Talanta 2009, 78, 711.

In a limited set of experiments, we have also tested RTILs in otherwisesimilar composites, and have not seen similar results to those weobtained with GUMBOS-based composites (data not shown). Without wishingto be bound by this hypothesis, we believe that the differences are dueto the better ability of GUMBOS than RTILs to make gel-like compositeswith appropriate properties.

Examples 15-20 Response of Prototype Sensor Towards Six Gaseous Analytes

We investigated the response of the novel GUMBOS composite-coated QCMsensor towards six gaseous analytes: acetonitrile, acetone, chloroform,methanol, ethanol, and toluene. FIG. 4 depicts a plot of the frequencyshift as a function of vapor concentration for each of the six VOCs. Thesensor provided excellent linearity over a wide range of concentrations,as well as varying sensitivity to these chemically different organicvapors. The sensitivities, detection limits, and ranges studied aresummarized in Table 1.

TABLE 1 Detection limits, sensitivities, and ranges studied fordifferent VOCs Detection limit Range studied Sensitivity VOC (mg/L)(mg/L) (Hz · L/mg) acetone 0.0806 0.19-60.8 6.7 acetonitrile 0.02670.19-15.2 24.6 chloroform 0.1271 0.36-57.0 4.1 ethanol 0.1189 0.19-60.85.4 methanol 0.1611 0.19-61.1 3.8 toluene 0.0508 0.21-16.7 11.2

Example 21 Enhancing the Sensitivity and Selectivity

The sensitivity can be further enhanced by using a higher frequencyquartz resonator. In the Sauerbrey equation, the frequency shift isproportional to the square of the intrinsic frequency of the resonator.The sensitivity and selectivity can also be enhanced by employingdifferent GUMBOS, with different chemical properties. A major factorinfluencing the sensitivity is the interaction energy between theanalyte and the sorbent phase. Our MD simulations showed that the totalinteraction energy (electrostatic+van der Waals) experienced by amolecule differs from one analyte to another. The MD simulationspredicted that the order of the analyte-sorbent interaction energies forthe six analytes initially tested with the prototype [BM₂Im][PF₆]/CAcomposite film should be:acetonitrile>toluene>acetone>ethanol>methanol>chloroform. The predictedordering correlated closely with the ordering of the experimental slopesseen in FIG. 4. Interaction energies were expressed in units of kJ/mol,while the slopes had units of Hz/(mg/L). For comparison, the measuredvalues of the slopes were converted to moles of analyte absorbed per cm²for the same molar concentration of each vapor. Since Δf/(mg/L) isproportional to (moles/cm²)/(moles/L), the relative ordering remainedthe same.

Example 22 Other Sensor Characteristics

A rapid and reversible response that is consistent over time and afterrepeated exposures to analytes is a basic requirement for a viablesensor. FIG. 5 shows that the prototype sensor provided a stablebaseline, and exhibited complete regeneration after repeated exposure tochloroform vapors. (The other five compounds studied showed similarbehavior—data not shown.) FIG. 5 depicts the frequency and resistanceresponses of the sensor to four different concentrations of chloroformvapor over a course of time: (a) 17.8 mg/L, (b) 35.6 mg/L, (c) 53.4mg/L, and (d) 71.3 mg/L. The upper curve depicts motional resistance,and the lower curve depicts frequency. In each case, a liquid sample wasinjected into the chamber and allowed to vaporize. After equilibrium,the vapor was removed by flushing with ultra-high purity argon. Theamount of coating material on the QCR was 207 μg/cm².

The frequency baseline drift, which is normally a positive shift, wasfound to be minimal The system was considered to be in equilibrium whenthe drift held at less than ±2 Hz/hr. The noise level was below 0.2 Hz,and hence the minimum detectable signal (3×noise) was 0.6 Hz. Ascompared to values previously reported for an RTIL-based QCM sensor, thedetection limit was improved 46-fold for acetonitrile, 8.9-fold formethanol, and 8.1-fold for toluene. See I. Goubaidoulline, G. Vidrich,D. Johannsmann, Anal. Chem. 2005, 77, 615.

In order to estimate the response time, defined as the time to reach 99%of the stable value of the signal, chloroform vapors were introducedinto the measuring chamber. A very short analytical response time wasachieved, evidently less than one minute. See FIG. 8. However, precisemeasurement of the response time was not possible in these experimentsdue to complications introduced into the measurements by the time neededto fill the sample chamber. The regeneration time was apparentlysomewhat slower than the response time, but was also fast. Measurementof the regeneration time was likewise complicated by the time needed foranalyte vapor to clear from the chamber.

Example 23 Potential Applications in Sensor Arrays

A typical “real-world” sample contains a mixture of different volatileorganic compounds. Creating a single sensor that is capable ofaccurately discriminating a single compound from a complex mixture is asubstantial challenge. An alternative approach is to employ a sensorarray rather than a single sensor. A sensor array is a group ofcomplementary sensors that use pattern recognition or similar techniquesfor the identification or quantification of multiple analytes.Array-based detection systems do not require highly specific sensors.However, in general the various sensor elements should exhibit differentresponses to different analytes. The chemical sensitivity of a sensormaterial can be modulated by a change in its chemical structure. Sincechemically diverse GUMBOS may readily be synthesized by simply modifyingor changing the cationic and/or anionic components of the molecule,these compounds are well-suited for array-based gas sensingapplications.

Example 24 Determination of Molecular Weight, and Discrimination betweenDifferent Compounds

The composite-coated QCM can be used for molecular weight determinationand discrimination of organic vapors. FIG. 5 showed that the motionalresistance shift and the frequency shift were rapid, stable, andreversible. We have simultaneously measured Δf and ΔR for our prototypeQCM sensor upon exposure to each of the six compounds studied above, aswell as two additional analytes: 1-propanol, and tetrachloromethane. Theanalytes included both polar and non-polar compounds. FIG. 6( a) depictsa plot of Δf versus ΔR for each of these eight compounds. The plots werelinear over a wide range of vapor concentrations for each compound. Thedata presented in FIG. 6( a) were obtained under intermediate loadingconditions for the composite: 83 μg of composite film per cm² ofelectrode area. The analyte concentration ranges were: 1.93-77.0 mg/Lfor tetrachloromethane, 0.720-28.8 mg/L for chloroform, 0.209-8.36 mg/Lfor toluene, 0.194-11.7 mg/L for 1-propanol, 0.191-11.5 mg/L foracetone, 0.382-22.9 mg/L for ethanol, 0.190-4.75 mg/L for acetonitrile,and 0.574-23.0 mg/L for methanol. FIG. 9 depicts, for the same datagiven in FIG. 6( a), a plot of ΔR versus nanomoles of compound absorbedper square centimeter. Note in particular in FIG. 9 that ΔR was directlyproportional to the number of moles of analyte absorbed for a variety ofdifferent VOCs, regardless of the chemical nature of the individualcompounds.

FIG. 6( b) depicts a plot of the ratio Δf/ΔR versus molecular weight foreach of the eight compounds. These data points were obtained by takingthe ratio of Δf/ΔR at 6-8 different vapor concentrations within theranges shown in FIG. 6( a). This plot showed excellent linearity betweenΔf/ΔR and the molecular weight of the analytes, as demonstrated by thehigh correlation coefficient (r²>0.99). Error bars are included in FIG.6( b), but the magnitude of the standard deviations was so small thatthe error bars may be difficult to see. A slight deviation fromlinearity was consistently observed for acetone (M.W. 58), possibly dueto water vapor in the sample. The relationship between Δf/ΔR andmolecular weight can be expressed by the following equation:

$\begin{matrix}{\frac{\Delta \; f}{\Delta \; R} = {k \times {M.W.{+ C}}}} & \left( {{Equation}\mspace{14mu} 2} \right)\end{matrix}$

where k and C are constants, and M. W. is the molecular weight of theabsorbed species. From our data, C appeared to be equal to zero, withinexperimental error, leading to the simpler form:

$\begin{matrix}{\frac{\Delta \; f}{\Delta \; R} = {k \times {M.W.}}} & \left( {{Equation}\mspace{14mu} 2\; a} \right)\end{matrix}$

To the inventors' knowledge, a linear dependence between Δf and ΔR for agiven compound has not been previously reported. Nor has a lineardependence between the ratio Δf/ΔR and the molecular weight across arange of different compounds been previously reported. The simultaneousmeasurement of Δf and ΔR can thus be used to determine the molecularweights of compounds, and to help discriminate between different vapormolecules, irrespective of their concentrations. Note that themeasurement of either Δf alone or ΔR alone would not provide themolecular identity, because the response depends upon both theconcentration and the identity of the chemical species.

Example 25 Theoretical Basis for Sensor Behavior

Without wishing to be bound by the hypotheses given here, the inventorspropose the following theoretical explanation for the behavior andproperties of the novel sensors. We explain our observations usingconcepts of free volume and viscoelasticity. According to free-volumetheory, the unoccupied space (free volume) in solids and liquidscontains both “interstitial” free volume and “hole” free volume (i.e.,that for holes or vacancies). Another assumption of this theory is thatthe interstitial free volume is uniformly distributed, while holes orvacancies are discontinuously distributed throughout the material. It isthe “hole” free volume that is primarily responsible for moleculartransport. This theory has previously been applied primarily topolymers. However, the responses are likely to be different for GUMBOScomposites and polymers due to their structural differences.

G. Dlubek, Y. Yu, R. Krause-Rehberg, W. Beichel, S. Bulut, N. Pogodina,I. Krossing, C. Friedrich, J. Chem. Phys. 2010, 133, 124502 recentlydemonstrated the presence of subnanometer-size holes both in the solidand liquid states of ILs using positron annihilation lifetimespectroscopy. These holes are comparable in size to the size of theconstituting ions. The estimated hole density was 2.0×10²⁰ g⁻¹. Thesolubility and diffusion of gases in ILs have been explained using theconcept of ‘free volume’ or ‘void space’ available in these materials.The rapid response and recovery times observed for the novel sensor canbe attributed to the presence of free volumes that facilitate the rapiddiffusion of analyte molecules within the films.

Another aspect to consider is the viscoelastic behavior of ILs. W.Makino, R. Kishikawa, M. Mizoshiri, S. Takeda, M. Yao, J. Chem. Phys.2008, 129, 104510 demonstrated that alkyl imidazolium-based ILs havingsufficiently long side chains (≧C4) exhibit viscoelastic properties. Weattribute the observed motional resistance change for our composites tothe viscoelastic properties of these films. For viscoelastic materials,the shear modulus (G) can be represented as a complex quantity:G=G′+jG″, where G′ is shear storage modulus of the film, G″ is the shearloss modulus of the film, and j denotes the imaginary unit √{square rootover (−1)}. A review of the literature indicates that motionalresistance depends upon the following film parameters: shear modulus,thickness, mass density, and particle surface coverage. The viscoelasticproperties of polymer films have been extensively studied. For polymers,substantial changes in both G′ and G″ have been observed during vaporabsorption. The shear modulus is the more important parameterdetermining changes in motional resistance. For polymers it is knownthat vapor absorption induces film swelling, leading to an increase infree volume, a decrease in shear modulus, increased viscoelasticdamping, and increased motional resistance. Our data with the novelGUMBOS composites showed that the observed frequency shift was directlyproportional to the vapor phase concentration of the analytes (See,e.g., FIG. 4). The concentration of a compound in the sorbent phase, Cs,may be related to the concentration of the compound in the vapor phase,C_(v), through a partition constant K:

K=C _(s) /C _(v)  (Equation 3)

Equation 3, together with data such as shown in FIG. 4 imply that Δf isdirectly proportional to the mass of the compound absorbed into thefilm. This conclusion is consistent with the Sauerbrey equation.Equation 2 then implies that any motional resistance increase isdirectly proportional to the number of molecules of analyte absorbed,and that it is largely independent of the chemical properties of themolecules. See FIG. 9. This is believed to represent a novel discovery,never previously reported.

A simple theoretical analysis accounts, at least qualitatively, for ourexperimental observations. We assume that motional resistance increaseis due to changes in mass density, thickness, and shear modulus of thefilm, since these are the only parameters that should change duringvapor absorption. Because the amount of vapor absorbed is relatively low(the estimated maximum mass fraction of analyte in our experiments wasabout 0.01), the density of the sorbent-analyte system remainedessentially the same for all analytes, given an equal number of absorbedmolecules. Our MD simulations indicated that the total interactionenergy between an analyte molecule and other species present in thesystem (e.g., [BM₂Im]⁺, [PF₆]⁻ and CA), was much lower than the totalinteraction energy experienced by a typical cation, anion, or oligomerof CA in the same system. The MD results suggested that the VOCmolecules did not interact appreciably with the species in the sorbentmatrix. Because the analyte is present in low concentrations and doesnot interact strongly with the sorbent phase, it is possible that thevapor molecules behave more-or-less as an ideal gas within the freevolume of the sorbent matrix. Consequently, the same number of moleculesof analyte should produce similar thickness changes and free volumechanges, and should be more-or-less independent of the chemical identityof the analyte molecules. To a good approximation, the motionalresistance increase depends only on the number of molecules that areabsorbed. The free volume increase occurs primarily through holeexpansion and new hole formation.

Examples 26-28 Preliminary Experimental Studies using Other GUMBOS

We have also performed preliminary vapor sensing studies using threeother GUMBOS: 1-n-butyl-2,3-dimethylimidazoliumtrifluoromethanesulfonate ([BM₂Im][OTf]); 1-n-butyl-3-methylpyridiniumhexafluorophosphate ([BMPyr][PF₆]); and 1-ethyl-2,3-dimethylimidazoliumhexafluorophosphate ([EM₂Im][PF₆]). [BM₂Im][OTf] and [BMPyr][PF₆] showedsimilar behavior to that of [BM₂Im][PF₆]. By contrast, [EM₂Im][PF₆]exhibited decreased sensitivity, very slow response, and negligibleresistance changes. These observations supported our contention thatfree volume and viscoelasticity play an important role in determiningthe unique response observed for our sensor. We believe that[EM₂Im][PF₆] does not show appreciable viscoelastic behavior and hasless free volume due to a decrease in the length of the alkyl sidechain. We have also used another derivative of cellulose, celluloseacetate butyrate, with similar observations.

Properties that are desirable for the GUMBOS used in this inventioninclude: chemical stability, thermal stability, good glass transitiontemperature, and amphiphilicity—the ability to dissolve both hydrophobicand hydrophilic VOCs. Undesirable properties include: low stability,reactivity with VOCs (irreversible sorption), hygroscopicity. Coatingstability is most likely enhanced by forming a composite with a matrixmaterial such as cellulose acetate.

Example 29 Other GUMBOS that May be Used in this Invention

Ionic liquids typically comprise relatively bulky organic cations anddiffuse-charge inorganic anions such as PF₆ ⁻, BF₄ ⁻, Tf₂N⁻, or NO₃ ⁻,although in some ILs the anion is organic, or both cation and anion maybe organic. Typically, the ions are sterically mismatched, hinderingcrystal formation. The properties of ILs are highly “tunable,” allowingready modifications to meet specific needs by simple changes in thecation, the anion, or both. In addition, many ILs have useful propertiessuch as high thermal stability, non-flammability, and essentially zerovapor pressure.

“Frozen” IL nanoparticles have distinct properties from other types ofnanoparticles. ILs are broadly tunable by modifying the anionicconstituents, the cationic constituents, or both; meaning that manyproperties may readily be altered, such as melting point, density,viscosity, surface tension, solubility, tensile strength,hydrophobicity, hydrophilicity, rigidity, reactivity, radioactivity,magnetic properties, optical properties, and other physical and chemicalproperties. Some examples of high-melting-temperature (“frozen”) ILs aregiven in Tables 2 and 3 below, and other examples are known in the art.GUMBOS have a melting point between 25° C. and 250° C.

TABLE 2 Examples of Ionic Liquids with melting points 25-100° C. ExampleMP (° C.) Imidazolium- 1,3-Dimethylimidazolium 43 Basedtrifluoromethanesulfonate 1-Ethyl-3-methylimidazolium chloride 881-Ethyl-3-methylimidazolium bromide 65 1-Butyl-3-methylimidazoliumchloride 73 1-Ethyl-3-methylimidazolium tosylate 56 Pyridinium-N-Butyl-3,4-dimethylpyridinium chloride 72 BasedN-Butyl-4-methylpyridinium 44 hexafluorophosphate N-Butylpyridiniumhexafluorophosphate 75 Ammonium- Methyltrioctylammonium triflate 56based Tetraethylammonium tris 97 (pentafluoroethyl)trifluorophosphateTetrabutylammonium 92 bis(trifluoromethylsulfonyl)imide Pyrrolidinium-1-Butyl-1-methylpyrrolidinium 55 based bis[oxalato(2-)] bromide1-Butyl-1-methylpyrrolidinium 31 trifluoroacetate1-Butyl-1-methylpyrrolidinium 85 hexafluorophosphate Phosphonium-Trihexyltetradecylphosphonium 25 Based tetrafluoroborate Amino acid-Tetrabutyl ammonium alanate 76 based Alanine methyl ester lactate 38Alanine butyl ester tetrafluoroborate Fluorescent and Rhodamine B bis(trifluoromethane) 80 absorption dye- sulfonimide based CrystViolethexafluorophosphate 60 BasicYellow hexafluorophosphate 85 Methylviolet2Bbis (trifluoromethane) 48 sulfonimide MalachiteGreen hexafluorophosphate60 Near infra-red 1-Butyl-2-(2-{3-[2-(1-butyl-3,3-dimethyl- 52 dyes1,3-dihydro-indol-2-ylidene)-ethylidene]-2-chloro-cyclohex-1-enyl}-vinyl)-3,3- dimethyl-3H-indoliumbis(pentafluoroethylsulfonyl)imide1-Butyl-2-(2-{3-[2-(1-butyl-3,3-dimethyl- 871,3-dihydro-indol-2-ylidene)-ethylidene]-2-chloro-cyclohex-1-enyl}-vinyl)-3,3- dimethyl-3H-indolium tetraphenylborate 1-Butyl-2-(2-{3-[2-(1-butyl-3,3-dimethyl- 821,3-dihydro-indol-2-ylidene)-ethylidene]-2-chloro-cyclohex-1-enyl}-vinyl)-3,3- dimethyl-3H-indolium 3,5-bis(trifluoromethyl)phenyltrifluoroborate1-Butyl-2-(2-{3-[2-(1-butyl-3,3-dimethyl- 801,3-dihydro-indol-2-ylidene)-ethylidene]-2-chloro-cyclohex-1-enyl}-vinyl)-3,3- dimethyl-3H-indolium4-(trifluoromethyl) phenyltrifluoroborate1,3,3-Trimethyl-2-[7-(1,3,3-trimethyl-1,3- 98dihydro-indol-2-ylidene)-hepta-1,3,5- trienyl]-3H-indolium tetraphenylborate 1,3,3-Trimethyl-2-[7-(1,3,3-trimethyl-1,3- 99dihydro-indol-2-ylidene)-hepta-1,3,5- trienyl]-3H-indolium4-(trifluoromethyl) phenyltrifluoroborate1,3,3-Trimethyl-2-[7-(1,3,3-trimethyl-1,3- 72dihydro-indol-2-ylidene)-hepta-1,3,5- trienyl]-3H-indolium tetrakis[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2- propyl)phenyl]borate2-(2-{2-Chloro-3-[2-(1,3,3-trimethyl-1,3- 89dihydro-indol-2-ylidene)-ethylidene]-cyclohex-1-enyl}-vinyl)-1,3,3-trimethyl- 3H-indolium bis(trifluoromethane) sulfonimide 2-[2-[2-Chloro-3-[2-(1,3-dihydro-1,3,3-85 trimethyl-2H-indol-2-ylidene)-ethylidene]-1-cyclopenten-1-yl-ethenyl]-1,3,3- trimethyl-3H-indoliumhexafluorophosphate Vitamin-based Vitamin B4 lactate 100 Nicotinamideadenine dinucleotide lactate 40 Riboflavin 5′-adenosine diphosphate 40lactate Anti- Amantadine bis (trifluoromethane) 95 bacterial/viralsulfonimide compound- based See generally also: (1) the Ionic LiquidData Bank, NIST Standard Reference Database #147, currently availableonline at ilthermo.boulder.nist.gov; (2) H. Ohno et al., Accounts ofChemical Research. 2007, 40, 1122; and (3) M. Patil et al., Tetrahedron.2007, 63, 12702.

TABLE 3 Examples of Ionic Liquids with melting points 100-200° C.Example MP(° C.) Imidazolium- 1-Dodecyl-3-methylimidazolium 134 basedchloride 1-Ethyl-2,3-dimethylimidazolium 138 bromide1-Ethyl-2,3-dimethylimidazolium 110 trifluoromethanesulfonatePyridinium- N-Butylpyridinium bromide 105 basedN-Butyl-3-methylpyridinium chloride 117 N-Ethylpyridinium chloride 119Ammonium- Tetramethylammonium 130 based bis[oxalato(2-)] bromideTetramethylammonium tris 115 (pentafluoroethyl)trifluorophosphateTetramethylammonium 135 bis(trifluoromethanesulfonyl)imidePyrrolidinium- 1,1-Dimethylpyrrolidinium 107 basedtris(pentafluoroethyl) trifluorophosphate 1-Butyl-1-methylpyrrolidinium147 tetrafluoroborate Amino acid- Alanine butyl ester nitrate 104 basedAlanine butyl ester lactate 114 Fluorescent Rhodamine 6G nitrate 126dye- CrystalViolet 170 based bis(trifluoromethanesulfonyl)imide Thioflav169 bis(trifluoromethanesulfonyl)imide BasicYellow 127bis(trifluoromethanesulfonyl)imide Near infra-red1-Butyl-2-(2-{3-[2-(1-butyl-3,3- >120 dyes dimethyl-1,3-dihydro-indol-2-ylidene)-ethylidene]-2-chloro- cyclohex-1-enyl}-vinyl)-3,3-dimethyl-3H-indolium bis(trifluoromethanesulfonyl)imide1-Butyl-2-(2-{3-[2-(1-butyl-3,3- >120 dimethyl-1,3-dihydro-indol-2-ylidene)-ethylidene]-2-chloro- cyclohex-1-enyl}-vinyl)-3,3-dimethyl-3H-indolium trifluorophenylborate1,3,3-Trimethyl-2-[7-(1,3,3- >120 trimethyl-1,3-dihydro-indol-2-ylidene)-hepta-1,3,5-trienyl]-3H- indoliumbis(pentafluoroethylsulfonyl)imide 1,3,3-Trimethyl-2-[7-(1,3,3- >120trimethyl-1,3-dihydro-indol-2- ylidene)-hepta-1,3,5-trienyl]-3H-indolium bis(trifluoromethanesulfonyl)imide1,3,3-Trimethyl-2-[7-(1,3,3- >120 trimethyl-1,3-dihydro-indol-2-ylidene)-hepta-1,3,5-trienyl]-3H- indolium 3,5-bis(trifluoromethyl)phenyltrifluoro- borate1,3,3-Trimethyl-2-[7-(1,3,3- >120 trimethyl-1,3-dihydro-indol-2-ylidene)-hepta-1,3,5-trienyl]-3H- indolium tetrafluoroborate2-(2-{2-Chloro-3-[2-(1,3,3-trimethyl- >100 1,3-dihydro-indol-2-ylidene)-ethylidene]-cyclohex-1-enyl}-vinyl)- 1,3,3-trimethyl-3H-indoliumbis(pentafluoroethylsulfonyl)imide Vitamin-based1-Butyl-2-(2-{3-[2-(1-butyl-3,3- 140 dimethyl-1,3-dihydro-indol-2-ylidene)-ethylidene]-2-chloro- cyclohex-1-enyl}-vinyl)-3,3-dimethyl-3H-indolium bis(trifluoromethanesulfonyl)imide Anti-1-Butyl-2-(2-{3-[2-(1-butyl-3,3- 180 bacterial/viraldimethyl-1,3-dihydro-indol-2- compound- ylidene)-ethylidene]-2-chloro-based cyclohex-1-enyl}-vinyl)-3,3- dimethyl-3H-indoliumtrifluorophenylborate Additional ionic liquids that might be used in oneor more of the above applications include, for example: Rhod6G NO₃,CrystViol NTf₂, Thioflav NTf₂, BasicYellow NTf₂, VitB₄ PF₆ andTetracycline NTf₂.

MISCELLANEOUS

As used in the specification and claims, unless context clearlyindicates otherwise, an “ionic liquid” is a salt having a melting pointbelow about 250° C.; and in many cases is below about 100° C., so thatan aqueous solvent may be used in the synthesis. The term “ionic liquid”thus includes compositions that are, in fact, solids at temperaturesbelow their respective melting points. The term does not imply that thesalt is necessarily a liquid at any particular time; rather, it refersto the salt's melting point. Where an IL has a melting point above 100°C., higher boiling point solvents may be used such as glycerol,paraffin, mineral oil, and other solvents known in the art. Likewise,where a particular IL is water-soluble, then a nonaqueous solvent may beused for dispersal.

The melting point, according to the use for which the film is intended,may be chosen to greater than or equal to about: 25° C., 30° C., 35° C.,40° C., 45° C., 50° C., 55° C., 60° C., 65° C., 70° C., 75° C., 80° C.,85° C., 90° C., 95° C., 100° C., 105° C., 110° C., 115° C., 120° C.,125° C., 130° C., 135° C., 140° C., 145° C., 150° C., 155° C., 160° C.,165° C., 170° C., 175° C., 180° C., 185° C., 190° C., 195° C., 200° C.,205° C., 210° C., 215° C., 220° C., 225° C., 230° C., 235° C., 240° C.,or 245° C.

The melting point, according to the use for which the film is intended,may be chosen to less than or equal to about: 30° C., 35° C., 40° C.,45° C., 50° C., 55° C., 60° C., 65° C., 70° C., 75° C., 80° C., 85° C.,90° C., 95° C., 100° C., 105° C., 110° C., 115° C., 120° C., 125° C.,130° C., 135° C., 140° C., 145° C., 150° C., 155° C., 160° C., 165° C.,170° C., 175° C., 180° C., 185° C., 190° C., 195° C., 200° C., 205° C.,210° C., 215° C., 220° C., 225° C., 230° C., 235° C., 240° C., 245° C.,or 250° C.

An “organic salt” is a salt comprising at least one organic anion, or atleast one organic cation, or both an organic anion and an organiccation. Examples of organic ions that may be used include, for example:tosylate, trifluoromethanesulfonate,tris(pentafluoroethyl)trifluorophosphate,bis(trifluoromethylsulfonyl)imide, lactate, tetraphenyl borate,3,5-bis(trifluoromethyl)phenyltrifluoroborate, 4-(trifluoromethyl)phenyltrifluoroborate,tetrakis[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]borate, trifluorophenylborate, saccharin, acesulfame, fluorescein,eosin, and their respective derivatives.

The IL melting point is preferably higher than any temperatures at whichthe film will be used. In principle, there is no upper limit on what themelting point may be. As a practical matter, for many applications themelting point will be between about 25° C. and about 200° C. Forconvenience of handling and preparation, the melting point will often bebetween about 40° C. and about 100° C., a range that is appropriate formost of the applications discussed here.

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The complete disclosures of all references cited above and throughoutthe specification are hereby incorporated by reference in theirentirety, as are the complete disclosures of the two priorityapplications, Ser. No. 61/434,660 and Ser. No. 61/434,879. In the eventof an otherwise irresolvable conflict, however, the disclosure of thepresent specification shall control.

What is claimed:
 1. A composite material comprising an intermixture ofone or more GUMBOS with one or more polymers, wherein: (a) each of saidGUMBOS is an organic salt having a melting point between 25° C. and 250°C.; (b) said composite material is viscoelastic; and the viscoelasticcharacteristics of said composite material are substantially differentfrom what the viscoelastic characteristics of the GUMBOS alone would be,if the GUMBOS were not intermixed with the one or more polymers; (c)each of said one or more GUMBOS is amorphous within said compositematerial.
 2. The composite material of claim 1, wherein the rigidity ofsaid composite material is substantially different from the rigiditythat the GUMBOS alone would possess, if the GUMBOS were not intermixedwith the one or more polymers.
 3. An article of manufacture, comprisinga piezoelectric crystal coated with a film, wherein said film comprisesthe composite material of claim
 1. 4. The article of manufacture ofclaim 3, wherein said piezoelectric crystal comprises quartz.
 5. Thearticle of manufacture of claim 3 wherein, following the absorption ofgas molecules by said film, the change in the motional resistance ofsaid piezoelectric crystal is a linear function of the number ofabsorbed gas molecules, and the change in the motional resistance ofsaid piezoelectric crystal is independent of the chemical properties ofthe absorbed gas molecules.
 6. A crystal microbalance comprising thearticle of manufacture of claim
 5. 7. A method of detecting one or morevolatile organic compounds with the crystal microbalance of claim 6,said method comprising measuring changes in the motional resistance ofthe piezoelectric crystal in the presence of the one or more volatileorganic compounds, or measuring changes in the frequency of thepiezoelectric crystal in the presence of the one or more volatileorganic compounds, or both; wherein a change in the motional resistanceor a change in the frequency indicates that one or more volatilecompounds have been absorbed by the film.
 8. An array comprising aplurality of the crystal microbalances of claim 6, wherein each of saidcrystal microbalances comprises a film of a different said compositematerial, wherein the different said crystal microbalances possessdiffering sensitivities to different compounds; whereby the selectivityof the array to discriminate between different compounds is enhanced ascompared to the selectivity of any of the individual said crystalmicrobalances.
 9. A method of determining the molecular weight, M. W.,of a volatile organic compound with the crystal microbalance of claim 6,said method comprising measuring the change, ΔR, in the motionalresistance of the piezoelectric crystal in the presence of the volatileorganic compound, and measuring the change, Δf, in the frequency of thepiezoelectric crystal in the presence of the volatile organic compound;and calculating M.W.=Δf/(k·ΔR); wherein k is a proportionality constantthat is characteristic of the crystal microbalance, the composition ofthe composite, and the mass of the film per unit area on the surface ofthe piezoelectric crystal; and wherein the proportionality constant k isindependent of the chemical properties of the volatile organic compound.